WO2019048843A2 - POLYMERIZATION OF OLEFINS - Google Patents

POLYMERIZATION OF OLEFINS Download PDF

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Publication number
WO2019048843A2
WO2019048843A2 PCT/GB2018/052503 GB2018052503W WO2019048843A2 WO 2019048843 A2 WO2019048843 A2 WO 2019048843A2 GB 2018052503 W GB2018052503 W GB 2018052503W WO 2019048843 A2 WO2019048843 A2 WO 2019048843A2
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Prior art keywords
alkyl
halo
alkoxy
amino
optionally substituted
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PCT/GB2018/052503
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English (en)
French (fr)
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WO2019048843A3 (en
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Charlotte Katherine WILLIAMS
Christopher Blair DURR
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Scg Chemicals Co., Ltd.
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Priority to US16/644,341 priority Critical patent/US20210079029A1/en
Priority to KR1020207009691A priority patent/KR20200042950A/ko
Priority to CN201880071267.6A priority patent/CN111655743A/zh
Priority to JP2020533375A priority patent/JP2020532641A/ja
Priority to EP18766030.3A priority patent/EP3679073A2/en
Publication of WO2019048843A2 publication Critical patent/WO2019048843A2/en
Publication of WO2019048843A3 publication Critical patent/WO2019048843A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/64003—Titanium, zirconium, hafnium or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/64006—Bidentate ligand
    • C08F4/64041—Monoanionic ligand
    • C08F4/64048—NO
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/64003—Titanium, zirconium, hafnium or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/64006—Bidentate ligand
    • C08F4/64041—Monoanionic ligand
    • C08F4/64058—OO
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • the present invention relates to the use of catalytic compounds in the polymerisation of olefins. More particularly, the present invention relates to the use of catalytic compounds in the homopolymerisation or copolymerisation of olefins (e.g. ethene).
  • olefins e.g. ethene
  • a particular group of these Ziegler-Natta type catalysts which catalyse the polymerization of ethylene (and a-olefins in general), comprise an aluminoxane activator and a metallocene transition metal catalyst.
  • Metallocenes comprise a metal bound between two ⁇ 5 - cyclopentadienyl type ligands.
  • the r -cyclopentadienyl type ligands are selected from r -cyclopentadienyl, n , 5 -indenyl and n , 5 -fluorenyl.
  • CGCs constrained geometry complexes
  • a process for the polymerisation of at least one olefin comprising the step of contacting the at least one olefin with a compound having a structure according to formula (l-A), (l-B) or (l-C) defined herein.
  • (m-nC) or "(m-nC) group” used alone or as a prefix, refers to any group having m to n carbon atoms.
  • alkyl refers to straight or branched chain alkyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms. This term includes reference to groups such as methyl, ethyl, propyl (n-propyl or isopropyl), butyl (n-butyl, sec-butyl or tert-butyl), pentyl, hexyl and the like. In particular, an alkyl may have 1 , 2, 3 or 4 carbon atoms.
  • alkenyl refers to straight or branched chain alkenyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms.
  • This term includes reference to groups such as ethenyl (vinyl), propenyl (allyl), butenyl, pentenyl and hexenyl, as well as both the cis and trans isomers thereof.
  • alkynyl refers to straight or branched chain alkynyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms.
  • the term includes reference to alkynyl moieties containing 1 , 2 or 3 carbon-carbon triple bonds (C ⁇ C). This term includes reference to groups such as ethynyl, propynyl, butynyl, pentynyl and hexynyl.
  • haloalkyl refers to alkyl groups being substituted with one or more halogens (e.g. F, CI, Br or I). This term includes reference to groups such as 2- fluoropropyl, 3-chloropentyl, as well as perfluoroalkyl groups, such as perfluoromethyl.
  • alkoxy refers to -O-alkyl, wherein alkyl is straight or branched chain and comprises 1 , 2, 3, 4, 5 or 6 carbon atoms. In one class of embodiments, alkoxy has 1 , 2, 3 or 4 carbon atoms. This term includes reference to groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like.
  • dialkylamino as used herein means a group -N(RA)(RB), wherein RA and RB are alkyl groups.
  • aryl or “aromatic” as used herein means an aromatic ring system comprising 6, 7, 8, 9 or 10 ring carbon atoms. Aryl is often phenyl but may be a polycyclic ring system, having two or more rings, at least one of which is aromatic. This term includes reference to groups such as phenyl, naphthyl and the like. Unless otherwise specification, aryl groups may be substituted by one or more substituents. A particularly suitable aryl group is phenyl.
  • aryloxy refers to -O-aryl, wherein aryl has any of the definitions discussed herein. Also encompassed by this term are aryloxy groups in having an alkylene chain situated between the O and aryl groups.
  • heteroaryl or “heteroaromatic” means an aromatic mono-, bi-, or polycyclic ring incorporating one or more (for example 1-4, particularly 1 , 2 or 3) heteroatoms selected from nitrogen, oxygen or sulfur.
  • heteroaryl groups are monocyclic and bicyclic groups containing from five to twelve ring members, and more usually from five to ten ring members.
  • the heteroaryl group can be, for example, a 5- or 6-membered monocyclic ring or a 9- or 10-membered bicyclic ring, for example a bicyclic structure formed from fused five and six membered rings or two fused six membered rings.
  • Each ring may contain up to about four heteroatoms typically selected from nitrogen, sulfur and oxygen.
  • the heteroaryl ring will contain up to 3 heteroatoms, more usually up to 2, for example a single heteroatom.
  • heteroaryloxy refers to -O-heteroaryl, wherein heteroaryl has any of the definitions discussed herein. Also encompassed by this term are heteroaryloxy groups in having an alkylene chain situated between the O and heteroaryl groups.
  • Carbocyclyl means a non-aromatic saturated or partially saturated monocyclic, or a fused, bridged, or spiro bicyclic carbocyclic ring system(s).
  • Monocyclic carbocyclic rings contain from about 3 to 12 (suitably from 3 to 7) ring atoms.
  • Bicyclic carbocycles contain from 7 to 17 carbon atoms in the rings, suitably 7 to 12 carbon atoms, in the rings.
  • Bicyclic carbocyclic rings may be fused, spiro, or bridged ring systems.
  • a particularly suitable carbocyclic group is adamantyl.
  • heterocyclyl means a non-aromatic saturated or partially saturated monocyclic, fused, bridged, or spiro bicyclic heterocyclic ring system(s).
  • Monocyclic heterocyclic rings contain from about 3 to 12 (suitably from 3 to 7) ring atoms, with from 1 to 5 (suitably 1 , 2 or 3) heteroatoms selected from nitrogen, oxygen or sulfur in the ring.
  • Bicyclic heterocycles contain from 7 to 17 member atoms, suitably 7 to 12 member atoms, in the ring.
  • Bicyclic heterocyclic(s) rings may be fused, spiro, or bridged ring systems.
  • halogen refers to F, CI, Br or I. In a particular, halogen may be F or CI, of which CI is more common.
  • substituted as used herein in reference to a moiety means that one or more, especially up to 5, more especially 1 , 2 or 3, of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents.
  • optionally substituted as used herein means substituted or unsubstituted.
  • a process for the polymerisation of at least one olefin comprising the step of contacting the at least one olefin with a compound having a structure according to formula (l-A), (l-B) or (l-C) shown below:
  • M is a Group IV transition metal
  • each X is independently selected from halo, hydrogen, a phosphonate, sulfonate or boronate group, (1-4C)dialkylamino, (1-6C)alkyl, (1-6C)alkoxy, aryl, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1- 6C)alkoxy, aryl and Si[(1-4C)alkyl] 3 ,
  • R2 is absent or is selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1 - 6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl and (1-6C)alkoxy,
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1- 6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl and (1-6C)alkoxy,
  • R 7 is selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, aryl, heteroaryl, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1- 6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl and (1-6C)alkoxy,
  • Ri is a group having the formula (II) shown below: (II) wherein
  • R a is selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1- 6C)haloalkyl, (1-6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl,
  • L is a group -[C(R x ) 2 ]n- wherein
  • each Rx is independently selected from hydrogen, (1- 6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1- 6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1- 6C)haloalkyl and aryl, and
  • n 0,1 , 2, 3 or 4.
  • the new family of catalysts encompasses three different coordination chemistry, embodied by formulae (l-A), (l-B) and (l-C).
  • formula (l-A) both bidentate phenyl-containing ligands are bound to M via two oxygen atoms (0,0.0,0 coordination), thereby forming two 5-membered rings.
  • formula (l-B) one of the phenyl-containing ligands is bound to M via two oxygen atoms, whereas the other phenyl-containing ligand is bound to M via one oxygen atom and one nitrogen atom ( ⁇ , ⁇ . ⁇ , ⁇ coordination), thereby forming one 5- membered ring and one 6-membered ring.
  • formula (l-C) both bidentate phenyl-containing ligands are bound to M via one oxygen atom and one nitrogen atom ( ⁇ , ⁇ . ⁇ , ⁇ coordination), thereby forming two 6-membered rings.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A) or (l-B).
  • the particular coordination type depicted in formulae (l-A) and (l-B) is preferred.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A).
  • the particular coordination type depicted in formula (l-A) is most preferred.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-B).
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-C).
  • the compound has a structure according to formula (l-A), (l-B) or (I- C), wherein
  • M is a Group IV transition metal
  • each X is independently selected from halo, hydrogen, a phosphonate, sulfonate or boronate group, (1-6C)alkyl, (1-6C)alkoxy, aryl, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl and Si[(1-4C)alkyl] 3 ,
  • R2 is absent or is selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1- 6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl and (1-6C)alkoxy,
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1- 6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl and (1-6C)alkoxy
  • R 7 is selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, aryl, heteroaryl, carbocyclyl and heterocyclyl, any of
  • Ri is a group having the formula (II) shown below:
  • R a is selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1- 6C)haloalkyl, (1-6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl,
  • L is a group -[C(R x ) 2 ]n- wherein
  • each Rx is independently selected from hydrogen, (1- 6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1- 6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1- 6C)haloalkyl and aryl, and
  • n 0, 1 , 2, 3 or 4.
  • M is selected from titanium, zirconium and hafnium.
  • M is selected from titanium and zirconium. More suitably, M is titanium.
  • each X is independently selected from halo, hydrogen, (1- 4C)dialkylamino, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl and Si[(1-4C)alkyl] 3 .
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1- 6C)alkoxy, aryl and Si[(1-4C)alkyl] 3 .
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl.
  • each X is independently selected from halo, hydrogen, (1-4C)alkoxy, and phenoxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy and phenyl.
  • each X is independently selected from halo, hydrogen, -N(CH3)2, - N(CH2CH3)2 and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy.
  • each X is independently selected from halo, hydrogen, and (1- 4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy.
  • each X is independently selected from chloro, bromo, -N(CH3)2, - N(CH 2 CH 3 ) 2 and (1-4C)alkoxy.
  • each X is independently selected from chloro, bromo and (1- 4C)alkoxy.
  • each X is independently (1-4C)alkoxy.
  • each X is isopropoxy.
  • each X is independently (1-4C)dialkylamino.
  • X is independently -N(CH 3 ) 2 or -N(CH 2 CH 3 ) 2 .
  • R2 is absent or is selected from hydrogen, hydroxy, (1-6C)alkyl, (2- 6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, (1-6C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1- 4C)haloalkyl and (1-4C)alkoxy.
  • R2 is absent or is selected from hydrogen, hydroxy, (1-4C)alkyl, (2- 4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy.
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and aryl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy.
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy.
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl.
  • R2 is absent or is selected from hydrogen and (1-4C)alkyl.
  • R2 is absent or hydrogen.
  • R2 is absent.
  • R2 is hydrogen
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1- 4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl and (1-4C)alkoxy.
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy.
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl.
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl.
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl.
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, (1-4C)alkyl and phenyl. [0062] In an embodiment, R3 IS hydrogen.
  • R3, R 4 , 5 and R6 are hydrogen.
  • R 7 is selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1- 6C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl and (1- 6C)alkoxy.
  • R 7 is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1- 4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1- 4C)alkoxy.
  • R 7 is selected from (1-4C)alkyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy.
  • R 7 is selected from (1-4C)alkyl and aryl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1 - 4C)alkyl and (1-4C)alkoxy.
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1- 4C)alkyl.
  • the one or more optional substituents is halo (e.g. fluoro).
  • R 7 is (1-2C)alkyl, optionally substituted with one or more substituents selected from halo.
  • R 7 is (1-2C)alkyl.
  • R 7 is methyl, optionally substituted with one or more fluoro substituents.
  • R 7 is methyl or trifluoromethyl.
  • R 7 is methyl
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1- 4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl.
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1- 4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1- 6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy.
  • R a is selected from (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy.
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1- 6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy.
  • R a is selected from phenyl, phenoxy, 5-7 membered heteroaryl, 5-7 membered heteroaryloxy, 5-12 membered carbocyclyl and 5-12 membered heterocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-5C)alkyl, (1-5C)haloalkyl, phenyl, phenoxy, heteroaryl and heteroaryloxy.
  • R a is selected from phenyl, 5-7 membered heteroaryl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1- 5C)alkyl, (1-5C)haloalkyl, phenyl, and heteroaryl.
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-5C)haloalkyl, phenyl, and heteroaryl.
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1-5C)alkyl, phenyl, and heteroaryl.
  • R a is not unsubstituted phenyl or unsubstituted cyclohexyl.
  • R a is not unsubstituted phenyl.
  • R a is not unsubstituted cyclohexyl.
  • R x is independently selected from hydrogen, (1-6C)alkyl, (1- 6C)alkoxy and aryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl and (1-6C)haloalkyl.
  • R x is independently selected from hydrogen, (1-4C)alkyl, (1- 4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-6C)alkyl.
  • R x is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl.
  • each R x is phenyl
  • n 0, 1 or 2.
  • n is 0 or 1.
  • n is 0 (in which case R a is bonded directly to N).
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A), (l-B) or (l-C), wherein
  • M is selected from titanium, zirconium and hafnium
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • R 7 is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1 -4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and
  • n 0, 1 or 2.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A), (l-B) or (l-C), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from halo, hydrogen, and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl, (1- 4C)haloalkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-4C)alkyl and aryl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A), (l-B) or (l-C), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo and (1-4C)alkoxy;
  • R2 is absent or is selected from hydrogen and (1-4C)alkyl
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A), (l-B) or (l-C), wherein
  • M is titanium
  • each X is independently (1-4C)alkoxy
  • R2 is absent
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, (1-4C)alkyl and phenyl; R 7 is (1-2C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-1), (l-B-1) or (l-C-1) shown below:
  • M, X, Ri and R3-R7 have any of the definitions discussed hereinbefore in respect of formulae (l-A), (l-B) and (l-C).
  • the compound having a structure according to formula (l-A-1), (l-B-1 ) or (l-C-1 ) has a structure according to formula (l-A-1) or (l-B-1).
  • the compound having a structure according to formula (l-A-1), (l-B-1 ) or (l-C-1 ) has a structure according to formula (l-A-1).
  • the compound having a structure according to formula (l-A-1), (l-B-1) or (l-C-1) has a structure according to formula (l-B-1).
  • the compound having a structure according to formula (l-A- 1), (l-B-1) or (l-C-1) has a structure according to formula (l-C-1).
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-1), (l-B-1) or (l-C-1), wherein
  • M is selected from titanium, zirconium and hafnium
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R 4 , 5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • R 7 is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1 -4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and
  • n 0, 1 or 2.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-1), (l-B-1) or (l-C-1), wherein
  • M is selected from titanium and zirconium; each X is independently selected from halo, hydrogen, and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R 4 , 5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl, (1- 4C)haloalkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-4C)alkyl and aryl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-1), (l-B-1) or (l-C-1), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo and (1-4C)alkoxy;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl; and
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-1), (l-B-1) or (l-C-1), wherein
  • M is titanium
  • each X is independently (1-4C)alkoxy
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, (1-4C)alkyl and phenyl; R 7 is (1-2C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-2), (l-B-2) or (l-C-2) shown below:
  • M, X and R1-R6 have any of the definitions discussed hereinbefore in respect of formulae (l-A), (l-B) and (l-C).
  • the compound having a structure according to formula (l-A- 2), (l-B-2) or (l-C-2) has a structure according to formula (l-A-2) or (l-B-2).
  • the compound having a structure according to formula (l-A- 2), (l-B-2) or (l-C-2) has a structure according to formula (l-A-2).
  • the compound having a structure according to formula (l-A- 2), (l-B-2) or (l-C-2) has a structure according to formula (l-B-2).
  • the compound having a structure according to formula (l-A- 2), (l-B-2) or (l-C-2) has a structure according to formula (l-C-2).
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-2), (l-B-2) or (l-C-2), wherein
  • M is selected from titanium, zirconium and hafnium; each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , 5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and
  • n 0, 1 or 2.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-2), (l-B-2) or (l-C-2), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from halo, hydrogen, and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl, (1- 4C)haloalkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-2), (l-B-2) or (l-C-2), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo and (1-4C)alkoxy;
  • R2 is absent or hydrogen
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-2), (l-B-2) or (l-C-2), wherein
  • M is titanium
  • each X is independently (1-4C)alkoxy
  • R2 is absent or hydrogen
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, (1-4C)alkyl and phenyl;
  • Ri is a group of formula (II) defined herein, wherein R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-2), (l-B-2) or (l-C-2), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo and (1-4C)alkoxy;
  • R2 is absent
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-2), (l-B-2) or (l-C-2), wherein
  • M is titanium
  • each X is independently (1-4C)alkoxy
  • R2 is absent or hydrogen
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, (1-4C)alkyl and phenyl; Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl; each Rx is phenyl; and
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-3), (l-B-3) or (l-C-3) shown below:
  • the compound having a structure according to formula (l-A-3), (l-B- 3) or (l-C-3) has a structure according to formula (l-A-3) or (l-B-3).
  • the compound having a structure according to formula (l-A-3), (l-B- 3) or (l-C-3) has a structure according to formula (l-A-3).
  • the compound having a structure according to formula (l-A-3), (l-B- 3) or (l-C-3) has a structure according to formula (l-B-3).
  • the compound having a structure according to formula (l-A-3), (l-B- 3) or (l-C-3) has a structure according to formula (l-C-3).
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-3), (l-B-3) or (l-C-3), wherein
  • M is selected from titanium, zirconium and hafnium
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R 7 is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and
  • n 0, 1 or 2.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-3), (l-B-3) or (l-C-3), wherein
  • M is selected from titanium and zirconium; each X is independently selected from halo, hydrogen, and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-3), (l-B-3) or (l-C-3), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo and (1-4C)alkoxy;
  • R2 is absent or hydrogen
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-3), (l-B-3) or (l-C-3), wherein M is selected from titanium and zirconium;
  • each X is independently selected from chloro, bromo and (1-4C)alkoxy;
  • R2 is absent
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-3), (l-B-3) or (l-C-3), wherein
  • M is titanium
  • each X is independently (1-4C)alkoxy
  • R2 is absent or hydrogen
  • R 7 is (1-2C)alkyl
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-3), (l-B-3) or (l-C-3), wherein
  • M is titanium
  • each X is independently (1-4C)alkoxy
  • R2 is absent; R 7 is (1-2C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A) or (l-B), wherein
  • M is selected from titanium, zirconium and hafnium
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • R 7 is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1 -4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and
  • n 0, 1 or 2.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A) or (l-B), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from halo, hydrogen, and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl, (1- 4C)haloalkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-4C)alkyl and aryl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A) or (l-B), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo and (1-4C)alkoxy;
  • R2 is absent or is selected from hydrogen and (1-4C)alkyl
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-3C)alkoxy, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A) or (l-B), wherein
  • M is titanium
  • each X is independently (1-4C)alkoxy
  • R2 is absent
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, (1-4C)alkyl and phenyl; R 7 is (1-2C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound has a structure according to formula (l-A) or (l-B), wherein
  • M is selected from titanium, zirconium and hafnium
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, (1-4C)dialkylamino and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • R 7 is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1 -4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and
  • n 0, 1 or 2.
  • the compound has a structure according to formula (l-A) or (l-B), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from halo, hydrogen, (1-4C)dialkylamino and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl, (1- 4C)haloalkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-4C)alkyl and aryl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy; Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl; and
  • n 0 or 1.
  • the compound has a structure according to formula (l-A) or (l-B), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo, (1-2C)dialkylamino and (1-4C)alkoxy; R2 is absent or is selected from hydrogen and (1-4C)alkyl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-3C)alkoxy, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound has a structure according to formula (l-A) or (l-B), wherein
  • M is titanium
  • each X is independently (1-2C)dialkylamino or (1-4C)alkoxy;
  • R2 is absent
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, (1-4C)alkyl and phenyl; R 7 is (1-2C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-1) or (l-B-1), wherein
  • M is selected from titanium, zirconium and hafnium
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • R 7 is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1 -4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and
  • n 0, 1 or 2.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-1) or (l-B-1), wherein
  • M is selected from titanium and zirconium; each X is independently selected from halo, hydrogen, and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R 4 , 5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl, (1- 4C)haloalkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-4C)alkyl and aryl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-1) or (l-B-1), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo and (1-4C)alkoxy;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-3C)alkoxy, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl; and
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-1) or (l-B-1), wherein
  • M is titanium
  • each X is independently (1-4C)alkoxy
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, (1-4C)alkyl and phenyl; R 7 is (1-2C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-1) or (l-B- 1), wherein
  • M is selected from titanium, zirconium and hafnium
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, (1-4C)dialkylamino and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • R 7 is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1 -4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and
  • n 0, 1 or 2.
  • the compound has a structure according to formula (l-A-1) or (l-B- 1), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from halo, hydrogen, (1-4C)dialkylamino and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl, (1- 4C)haloalkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-4C)alkyl and aryl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-1) or (l-B- 1), wherein
  • M is selected from titanium and zirconium; each X is independently selected from chloro, bromo, (1-2C)dialkylamino and (1-4C)alkoxy;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-3C)alkoxy, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-1) or (l-B-1), wherein
  • M is titanium
  • each X is independently (1-2C)dialkylamino or (1-4C)alkoxy;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, (1-4C)alkyl and phenyl; R 7 is (1-2C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-2) or (l-B-2), wherein
  • M is selected from titanium, zirconium and hafnium; each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , 5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and
  • n 0, 1 or 2.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-2) or (l-B-2), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from halo, hydrogen, and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl, (1- 4C)haloalkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-2) or (l-B-2), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo and (1-4C)alkoxy;
  • R2 is absent
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-3C)alkoxy, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-2) or (l-B-2), wherein
  • M is titanium
  • each X is independently (1-4C)alkoxy
  • R2 is absent
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, (1-4C)alkyl and phenyl;
  • Ri is a group of formula (II) defined herein, wherein R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-2) or (l-B- 2), wherein
  • M is selected from titanium, zirconium and hafnium
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, (1-4C)dialkylamino and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and
  • n 0, 1 or 2.
  • the compound has a structure according to formula (l-A-2) or (l-B- 2), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from halo, hydrogen, (1-4C)dialkylamino and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl, (1- 4C)haloalkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-2) or (l-B- 2), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo, (1-2C)dialkylamino and (1-4C)alkoxy; R2 is absent;
  • R3, R 4 , R5 and R6 are each independently selected from hydrogen, halo, amino, (1-4C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-3C)alkoxy, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-2) or (l-B- 2), wherein
  • M is titanium; each X is independently (1-2C)dialkylamino or (1-4C)alkoxy;
  • R2 is absent
  • R3, R 4 , 5 and R6 are each independently selected from hydrogen, (1-4C)alkyl and phenyl; Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-3) or (l-B-3), wherein
  • M is selected from titanium, zirconium and hafnium
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R 7 is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1 -4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and
  • n 0, 1 or 2.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-3) or (l-B-3), wherein M is selected from titanium and zirconium;
  • each X is independently selected from halo, hydrogen, and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-3) or (l-B-3), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo and (1-4C)alkoxy;
  • R2 is absent
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-3C)alkoxy, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-3) or (l-B-3), wherein
  • M is titanium
  • each X is independently (1-4C)alkoxy
  • R2 is absent
  • R 7 is (1-2C)alkyl
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-3) or (l-B- 3), wherein
  • M is selected from titanium, zirconium and hafnium
  • each X is independently selected from halo, hydrogen, (1-6C)alkoxy, (1-4C)dialkylamino and aryloxy, any of which may be optionally substituted one of more groups selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)haloalkyl, (1-6C)alkoxy and aryl;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R 7 is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, aryl and heteroaryl, any of which may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-4C)alkyl, (1-4C)haloalkyl and (1-4C)alkoxy;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)haloalkyl, (1-4C)alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, (1-4C)alkoxy and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1- 6C)alkyl; and n is 0, 1 or 2.
  • the compound has a structure according to formula (l-A-3) or (l-B- 3), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from halo, hydrogen, (1-4C)dialkylamino and (1-4C)alkoxy, any of which may be optionally substituted one of more groups selected from halo, hydroxy, amino, (1-4C)alkyl and (1-4C)alkoxy;
  • R2 is absent or is selected from hydrogen, (1-4C)alkyl and phenyl;
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from aryl, aryloxy, heteroaryl, heteroaryloxy, carbocyclyl and heterocyclyl, any of which (for example the aryl group) may be optionally substituted with one or more substituents selected from halo, oxo, hydroxy, amino, nitro, (1-6C)alkyl, (1-6C)alkoxy, (1-6C)haloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl;
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-3) or (l-B- 3), wherein
  • M is selected from titanium and zirconium
  • each X is independently selected from chloro, bromo, (1-2C)dialkylamino and (1-4C)alkoxy; R2 is absent;
  • R 7 is selected from (1-2C)alkyl and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, hydroxy, amino and (1-4C)alkyl;
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl and 5-12 membered carbocyclyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, hydroxy, amino, (1-5C)alkyl, (1-3C)alkoxy, (1-5C)haloalkyl, phenyl, and heteroaryl;
  • Rx is independently selected from hydrogen, (1-4C)alkyl, and phenyl, any of which may be optionally substituted with one or more substituents selected from halo, amino and (1-3C)alkyl; and
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-3) or (l-B- 3), wherein
  • M is titanium
  • each X is independently (1-2C)dialkylamino or (1-4C)alkoxy;
  • R2 is absent
  • R 7 is (1-2C)alkyl
  • Ri is a group of formula (II) defined herein, wherein
  • R a is selected from phenyl, cyclohexyl and adamantyl, any of which (for example the phenyl group) may be optionally substituted with one or more substituents selected from halo, (1- 5C)alkyl, phenyl, and heteroaryl;
  • each Rx is phenyl
  • n 0 or 1.
  • the compound has a structure according to formula (l-A-4a), (l-B- 4a) or (l-C-4a) shown below:
  • M is titanium or zirconium
  • each X is independently isopropoxide, ethoxide, N(CH3)2 or N(CH2CH3)2;
  • R2 is absent (in which case bond a is a double bond) or hydrogen (in which case bond a is a single bond);
  • R a is selected from perfluorophenyl, cyclohexyl, 2,6-dimethylphenyl, 2,6- diisopropylphenyl, biphenyl, adamantyl, 2,4,6-tritertbutylphenyl and trityl.
  • the compound has a structure according to formula (l-A-4a), (l-B- 4a) or (l-C-4a), wherein R2 is absent.
  • the compound has a structure according to formula (l-A-4a), (l-B- 4a) or (l-C-4a), wherein M is titanium and R a is selected from 2,6-diisopropylphenyl, biphenyl, adamantyl, 2,4,6-tritertbutylphenyl and trityl.
  • the compound has a structure according to formula (l-A-4a), (l-B- 4a) or (l-C-4a), wherein M is titanium and R a is selected from adamantyl, 2,4,6-tritertbutylphenyl and trityl.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-4b), (l-B-4b) or (l-C-4b) shown below:
  • M is titanium or zirconium
  • R a is selected from perfluorophenyl, cyclohexyl, 2,6- dimethylphenyl, 2,6-diisopropylphenyl, biphenyl, adamantyl, 2,4,6-tritertbutylphenyl and trityl.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-4b), (l-B-4b) or (l-C-4b), wherein M is titanium and R a is selected from 2,6-diisopropylphenyl, biphenyl, adamantyl, 2,4,6-tritertbutylphenyl and trityl.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-4b), (l-B-4b) or (l-C-4b), wherein M is titanium and R a is selected from adamantyl, 2,4,6-tritertbutylphenyl and trityl.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-4b), (l-B-4b) or (l-C-4b), wherein M is titanium and R a is selected from biphenyl and trityl.
  • the compound has a structure according to formula (l-A-4c), (l-B- 4c) or (l-C-4c) shown below:
  • M is titanium or zirconium
  • R v and R w are each independently methyl or ethyl
  • R2 is absent (in which case bond a is a double bond) or hydrogen (in which case bond a is a single bond);
  • R a is selected from perfluorophenyl, cyclohexyl, 2,6-dimethylphenyl, 2,6- diisopropylphenyl, biphenyl, adamantyl, 2,4,6-tritertbutylphenyl and trityl.
  • the compound has a structure according to formula (l-A-4c), (l-B- 4c) or (l-C-4c), wherein R2 is absent.
  • the compound has a structure according to formula (l-A-4c), (l-B- 4c) or (l-C-4c), wherein M is titanium and R a is selected from 2,6-diisopropylphenyl, biphenyl, adamantyl, 2,4,6-tritertbutylphenyl and trityl.
  • the compound has a structure according to formula (l-A-4c), (l-B- 4c) or (l-C-4c), wherein M is titanium and R a is selected from adamantyl, 2,4,6-tritertbutylphenyl and trityl.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-4c), (l-B-4c) or (l-C-4c), wherein M is titanium and R a is selected from 2,6-diisopropylphenyl, biphenyl, adamantyl and trityl.
  • the compound of formula (l-A), (l-B) or (l-C) has a structure according to formula (l-A-4c), (l-B-4c) or (l-C-4c), wherein M is titanium and R a is selected from biphenyl and trityl.
  • the compound of formula (l-A), (l-B) or (l-C) is immobilised on a supporting substrate.
  • the supporting substrate is a solid.
  • the compound may be immobilised on the supporting substrate by one or more covalent or ionic interactions, either directly, or via a suitable linking moiety. It will be appreciated that minor structural modifications resulting from the immobilisation of the compound of the supporting substrate (e.g. loss of one or both groups, X) are nonetheless within the scope of the invention.
  • the supporting substrate is selected from solid methyaluminoxane, silica, silica-supported methylaluminoxane, alumina, zeolite, layered double hydroxide and layered double hydroxide-supported methylaluminoxane.
  • the supporting substrate is solid methylaluminoxane.
  • solid MAO solid MAO
  • sMAO solid polymethylaluminoxane
  • solid polymethylaluminoxane any suitable solid polymethylaluminoxane may be used.
  • solid polymethylaluminoxane there exist numerous substantial structural and behavioural differences between solid polymethylaluminoxane and other (non-solid) MAOs. Perhaps most notably, solid polymethylaluminoxane is distinguished from other MAOs as it is insoluble in hydrocarbon solvents and so acts as a heterogeneous support system. The solid polymethylaluminoxane useful in the compositions of the invention are insoluble in toluene and hexane.
  • the aluminium content of the solid polymethylaluminoxane falls within the range of 36-41 wt%.
  • the solid polymethylaluminoxane useful as part of the present invention is characterised by extremely low solubility in toluene and n-hexane.
  • the solubility in n-hexane at 25°C of the solid polymethylaluminoxane is 0-2 mol%.
  • the solubility in n-hexane at 25°C of the solid polymethylaluminoxane is 0-1 mol%. More suitably, the solubility in n-hexane at 25°C of the solid polymethylaluminoxane is 0-0.2 mol%.
  • the solubility in toluene at 25°C of the solid polymethylaluminoxane is 0-2 mol%.
  • the solubility in toluene at 25°C of the solid polymethylaluminoxane is 0-1 mol%. More suitably, the solubility in toluene at 25°C of the solid polymethylaluminoxane is 0-0.5 mol%.
  • the solubility in solvents can be measured by the method described in JP- B(KOKOKU)-H07 42301.
  • the at least one olefin is at least one (2-10C)alkene.
  • the at least one olefin is at least one a-olefin.
  • the at least one olefin is ethene and optionally one or more other (3-10C)alkenes.
  • the polymerisation process is a copolymerisation process.
  • Suitable optional one or more other (3- 10C)alkenes include 1-hexene, styrene and methyl methacrylate.
  • the polymerisation process is a homopolymerisation process and the at least one olefin is ethene.
  • the mole ratio of the compound of formula (l-A), (l-B) or (l-C) to the at least one olefin is 1 :50 to 1 : 10,000.
  • the mole ratio of the compound of formula (l-A), (l-B) or (l-C) to the at least one olefin is 1 : 100 to 1 : 1000. More suitably, the mole ratio of the compound of formula (l-A), (l-B) or (l-C) to the at least one olefin is 1 : 150 to 1 :300.
  • the process is conducted in a solvent selected from toluene, hexane and heptane.
  • the process is conducted for a period of 1 minute to 96 hours.
  • the process is conducted for a period of 5 minute to 72 hours.
  • the process is conducted at a pressure of 0.9 to 10 bar.
  • the process is conducted at a pressure of 1.5 to 3 bar.
  • the process is conducted at a temperature of 30 to 120°C.
  • the process is conducted at a temperature of 40 to 100°C.
  • the process is conducted in the presence of an activator or co- catalyst.
  • the activator or co-catalyst is one or more organoaluminium compounds. Mores suitably, the one or more organoaluminium compounds are selected from alkylaluminoxane (e.g. methylaluminiumoxane), triisobutylaluminium and triethylaluminium.
  • the compounds of formula (l-A), (l-B) and (l-C) may be formed by any suitable process known in the art. Particular examples of processes for the preparation of compounds of formula (l-A), (l-B) and (l-C) are set out in the accompanying examples.
  • R1-R7 and bond a have any of the definitions appearing hereinbefore, with one equivalent of a compound of formula B shown below: (X) B wherein M and X have any of the definitions appearing hereinbefore in the presence of a suitable solvent.
  • Any suitable solvent may be used for step (i) of the process defined above.
  • a particularly suitable solvent is dry toluene.
  • Step (i) is suitably conducted at low temperature (e.g. ⁇ 0°C). More suitably, step (i) is conducted at a temperature of -80 to 0°C.
  • Other reaction conditions e.g. pressures, reaction times, agitation, etc.
  • R3-R7 have any of the definitions appearing hereinbefore, with a compound of formula D shown below:
  • Ri and R2 have any of the definitions appearing hereinbefore.
  • Step (i) is suitably conducted under refluxing conditions.
  • Other reaction conditions e.g. pressures, reaction times, agitation, etc.
  • Fig. 1 shows the 1 H NM R spectrum of H in CDC at 400 MHz
  • Fig. 2 shows the 1 H NM R spectrum of HL 2 in CDCb at 400 MHz
  • Fig. 3 shows the 1 H NM R spectrum of HL 3 in CDCb at 400 MHz
  • Fig. 4 shows the 1 H NM R spectrum of HL 4 in CDCb at 400 MHz
  • Fig. 5 shows the 1 H NM R spectrum of HL 5 in CDCb at 400 MHz
  • Fig. 6 shows the 1 H NM R spectrum of HL 6 in CDCb at 400 MHz
  • Fig. 7 shows the 1 H NM R spectrum of HL 7 in CDCb at 400 MHz
  • Fig. 8 shows the 1 H NM R spectrum of HL 8 in CDCb at 400 MHz
  • Fig. 9 shows the 1 H NM R spectrum of ⁇ CDCb at 400 MHz
  • Fig. 10 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of CDCb at 125 MHz
  • Fig. 12 shows the 1 H NMR spectrum of (L 2 ) 2 Ti(O i Pr) 2 in CDCb at 400 MHz
  • Fig. 14 shows the 1 H NMR spectrum of (L 3 ) 2 Ti(O i Pr) 2 in CDCb at 400 MHz
  • Fig. 15 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of in CDCb at 125 MHz
  • Fig. 17 shows the 1 H NMR spectrum of (U ⁇ T OPr ⁇ in CDCb at 400 MHz.
  • Fig. 18 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L ⁇ T ⁇ Pr ⁇ in CDCb at 125 MHz.
  • Fig. 21 shows the ⁇ NMR spectrum of (L 6 ) 2 Ti(O i Pr) 2 in CDCb at 400 MHz
  • Fig. 22 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 6 ) 2 Ti(O i Pr) 2 in CDCb at 125 MHz
  • Fig. 24 shows the 1 H NMR spectrum of (L 7 ) 2 Ti(O i Pr) 2 in CDCb at 400 MHz
  • Fig. 25 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 7 ) 2 Ti(O i Pr) 2 in CDCb at 125 MHz
  • Fig. 27 shows the 1 H NMR spectrum of (L 8 ) 2 Ti(O i Pr) 2 in CDCb at 400 MHz
  • Fig. 28 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 8 ) 2 Ti(O i Pr) 2 in CDCb at 125 MHz
  • Fig. 30 shows the 1 H NMR spectrum of (L ⁇ ZrC in CDCb at 400 MHz.
  • Fig. 31 shows the 1 H NMR spectrum of (Ls ⁇ ZrC in CDCb at 400 MHz.
  • Fig. 32 shows comparative 1 H NMR spectra of (Li) 2 Ti(O i Pr) 2 and H , in CDCb, 400 MHz.
  • Fig. 33 shows comparative 1 H NMR spectra of (L 4 ) 2 Ti(O i Pr) 2 and HL 4 , in CDCb, 400 MHz
  • Fig. 34 shows comparative 1 H NMR spectra of and HLy, in CDCI 3 , 400 MHz
  • Fig. 35 shows variable temperature NMR of the imine region of (l_4)2Ti(0'Pr)2 in cf-THF (500 MHz).
  • Fig. 36 shows variable high temperature 1 H NMR (500 MHz) of (L 4 ) 2 Ti(O i Pr) 2 in d 2 - tetrachloroethane
  • Fig. 37 shows 1 H NMR of (L 4 )2Ti(OPr)2 in d 2 -tetrachloroethane before heating (Top) and after heating for 24 h at 100 °C (bottom).
  • Fig. 38 shows variable low temperature 1 H NMR (500 MHz) of (L 4 ) 2 Ti(O i Pr) 2 in d 8 -THF
  • Fig. 39 shows 1 H NMR of (L 4 ) 2 Ti(O i Pr) 2 in d 8 -THF before heating (top) and after heating for 5 h at 70 °C (bottom).
  • Fig. 40 shows the 1 H NMR spectrum of HL 4 ' in CDC , 400 MHz.
  • Fig. 41 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of HL 4 ' in CDCb, 400 MHz.
  • Fig. 42 shows the 1 H NMR spectrum of HL 5 ' in CDCb, 400 MHz.
  • Fig. 43 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of HL 5 ' in CDCb, 400 MHz.
  • Fig. 44 shows the ⁇ NMR spectrum of HL 6 ' in CDCb, 400 MHz.
  • Fig. 45 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of HL 6 ' in CDCb, 400 MHz.
  • Fig. 46 shows the 1 H NMR spectrum of HLy' in CDCb, 500 MHz.
  • Fig. 47 shows the 1 H NMR spectrum of HL 4 F in CDCb, 400 MHz.
  • Fig. 48 shows the 1 H NMR spectrum of [(L F 4 ) 2 Ti(OPr) 2 ] in CDCb, 400 MHz, as well as the 19 F ⁇ 1 H ⁇ NMR spectrum comparing HL F 4 (-58.1 ppm) and [(L F 4 ) 2 Ti(OPr) 2 ] (-58.4) 400 MHz in CDCb.
  • Fig. 49 shows the ⁇ NMR spectrum of (L 4 ) 2 Ti(OEt) 2 in CDCb at 298 K.
  • Fig. 50 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 4 ) 2 Ti(OEt) 2 in CDCb at 298 K.
  • Fig. 51 shows the ⁇ NMR spectrum of (L 4 ') 2 Ti(O i Pr) 2 in CDCb at 298 K.
  • Fig. 52 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 4 ') 2 Ti(O i Pr) 2 in CDCb at 298 K.
  • Fig. 53 shows the 1 H NMR spectrum of (L 5 ') 2 Ti(OPr) 2 in CDCb at 298 K.
  • Fig. 54 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 6 ')2Tl(O i Pr)2 in CDCb at 298 K.
  • Fig. 55 shows the 1 H NMR spectrum of (U , )2Tl(O i Pr)2 in CDCb at 298 K.
  • Fig. 56 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 6 , )2Tl(O i Pr)2 in CDCb at 298 K.
  • Fig. 57 shows the 1 H NMR spectrum of (L 7 ')2Tl(O i Pr)2 in CDCb at 298 K. 400 MHz.
  • Fig. 58 shows X-ray crystal structures of (L4')2Ti(0'Pr)2 (left) and (L7')2Ti(0'Pr)2 (right) showing
  • Fig. 59 shows low temperature 1 H NMR spectrum of complex (L4')2Ti(0'Pr)2 in c ⁇ -THF (top) and high temperature 1 H NMR spectrum of complex (L4')2Ti(0'Pr)2 (bottom) in CeDe.
  • Fig. 60 shows Low temperature 1 H NMR of complex (L5')2Ti(0'Pr)2 (shown in its conjectured structure) in THF-d 8 (* THF or hexane) (top) and high temperature 1 H NMR of complex in C 6 D 6 (bottom).
  • Fig. 61 shows Low temperature 1 H NMR spectrum of complex (L6')2Ti(0'Pr)2 in c -THF (top) and high temperature 1 H NMR of complex (L6')2Ti(0'Pr)2 in CeDe (bottom).
  • Fig. 62 shows X-ray crystal structures of (L4)2Ti(OEt)2 (left), (L4)2Ti(0'Pr)2 (middle), and
  • Fig. 63 shows a) ethylene polymerization activity of catalysts (L TifO'Pr ⁇ in the slurry and solution phase, b) SEM of polyethylene derived from (L4')2Ti(0'Pr)2 immobilized on sMAO.
  • Fig. 64 shows (left) the ethylene homopolymerization activity of (L4,6)2Ti(0'Pr)2 and (L4')2Ti(0'Pr)2 at various temperatures and pressures; (right) the ethylene/1 -hexene copolymerization activity of (L4)2Ti(0'Pr)2 and (L TifO'Pr ⁇ at various temperatures.
  • Crystals suitable for single crystal x-ray diffraction were grown either through slow evaporation of hexanes into THF or through low temperature crystallization in concentrated THF at -30 °C.
  • Figure 1 shows the 1 H NMR spectrum of HLi in CDCb at 400 MHz.
  • o-Vanillin (2.75 g, 18.0 mmol) was added to a round bottom flask and dissolved in ethanol (30 mL). Cyclohexylamine (1.79 g, 18.0 mmol) was syringed into the stirring solution along with several drops of formic acid. Reaction mixture was refluxed for 18 hours resulting in an orange solution. Volatiles were removed under vacuum yielding a viscus yellow oil. The oil was placed in a -30 °C freezer to solidify into a soft yellow solid.
  • Figure 2 shows the 1 H NMR spectrum of HL 2 in CDCb at 400 MHz.
  • o-Vanillin (3 g, 19.7 mmol) was added to a round bottom flask and dissolved in ethanol (30 mL). 2,6-dimethylaniline (2.34 g, 19.7 mmol) was syringed into the stirring solution along with several drops of formic acid. Reaction mixture was refluxed for 18 hours resulting in a yellow solution. Upon removal of several mL of ethanol under vacuum yellow solid precipitated from solution. This solid was filtered and washed with pentane (3 X 20 mL). The resulting dark yellow powder was dried to remove residual solvent.
  • Figure 3 shows the 1 H NMR spectrum of HL 3 in CDCb at 400 MHz.
  • Figure 4 shows the 1 H NMR spectrum of HL 4 in CDCb at 400 MHz.
  • Figure 5 shows the 1 H NMR spectrum of HL 5 in CDCb at 400 MHz.
  • o-Vanillin (3 g, 19.7 mmol) was added to a round bottom flask and dissolved in ethanol (30 mL).
  • Adamantan-1-amine (2.98 g, 19.7 mmol) was then added to the stirring solution along with several drops of formic acid. Reaction mixture was refluxed for 20 hours resulting in an orange solution.
  • Figure 6 shows the 1 H NMR spectrum of HL 6 in CDCb at 400 MHz.
  • o-Vanillin 1.5 g, 9.86 mmol was added to a round bottom flask and dissolved in ethanol (30 ml_).
  • tritylamine (2.56 g, 9.86 mmol) was added into the stirring solution along with several drops of formic acid. This reaction mixture was refluxed for 24 hours resulting in a bright yellow precipitate and a pale yellow solution. Precipitate was filtered, washed with ethanol (30 ml_) and pentane (3 X 20 ml_) and dried under vacuum.
  • Figure 8 shows the 1 H NMR spectrum of HL 8 in CDCb at 400 MHz.
  • the o-vanillin derived ligands were found to possess two separate modes of coordination to the metal: 6-membered ⁇ /,0 coordination, and 5-membered 0,0 coordination. These two coordination modes were found to be independent of one another, thus the eight catalysts synthesized each exhibit one of three basic types of coordination chemistries found to be possible in these systems. Type A: N,0:N,0 coordination, Type B: N, 0:0,0 coordination, Type C: 0,0:0,0 coordination. Within each type there are also additional isomers that are theoretically possible. Upon increasing steric bulk, coordination around the metal centre rearranges from: Type A-l to Type A-ll, then to Type B followed by Type C. (Scheme 3).
  • Hl_i (0.50 g, 1.58 mmol) and (0.224 g, 0.79 mmol) were dissolved separately in toluene (7 mL and 3 mL, respectively), and cooled to -30 °C in a glovebox freezer. The two solutions were then mixed and allowed to stir for 18 hours. Volatiles were removed in vacuo yielding a bright orange solid. Yield: 316 mg (50%) MALDI-TOF MS (m/z): 739.64 (calc.
  • Figure 9 shows the ⁇ NMR spectrum of CDCb at 400 MHz.
  • Figure 10 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of CDCb at 125 MHz.
  • HL2 (0.30 g, 1.29 mmol) and Ti(O i Pr) 4 (0.183 g, 0.643 mmol) were dissolved separately in toluene (15 mL and 5 mL, respectively), and cooled to -30 °C in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours turning from yellow to light orange. Volatiles were removed in vacuo and hexane (30 mL) was added to the resulting orange-yellow wax. Crude mixture was recrystallized from a minimum of THF in a -30 °C freezer. Crude Yield: 332 mg (82%) MALDI-TOF MS (m/z): 571 .3003 (calc.
  • Figure 12 shows the ⁇ NMR spectrum of ( ⁇ 2) 2 ⁇ (0 ! ⁇ ) 2 in CDCI3 at 400 MHz.
  • Hl_3 (0.246 g, 0.964 mmol) and (0.137 g, 0.482 mmol) were dissolved separately in toluene (15 mL and 5 mL, respectively), and cooled to -30 °C in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo and hexane (10 mL) was added to the resulting orange-yellow wax. This hexane was removed under vacuum to provide the final complex as a bright orange powder. Yield: 327 mg (99%).
  • MALDI-TOF MS (m/z): 615.3101 (calc.
  • Figure 14 shows the 1 H NMR spectrum of (L 3 ) 2 Ti(O i Pr) 2 in CDCb at 400 MHz
  • Figure 15 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 3 ) 2 Ti(O i Pr) 2 in CDCb at 125 MHz.
  • Figure 16 shows the ORTEP representation of (L3) 2 Ti(0'Pr) 2 .
  • (L3) 2 Ti(0'Pr) 2 Upon increasing steric hindrance to form (L3) 2 Ti(0'Pr) 2 a rearrangement is observed from Type A-l to Type A-ll where imine nitrogens prefer a trans geometry. In this arrangement, steric pressure is relieved by creating space between R groups while still maintaining 0, N:0, N coordination. As a result of this rearrangement, the Ti - N bond distances shorten and Ti - O distances elongate by -0.08 A compared to (L 2 ) 2 Ti(O i Pr) 2 . Synthesis of (L 4 ) 2 Ti(OPr)
  • Hl_4 (0.30 g, 0.946 mmol) and (0.137 g, 0.482 mmol) were dissolved separately in toluene (15 mL and 5 mL, respectively), and cooled to -30 °C in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo and hexane (10 mL) was added to the resulting orange-yellow wax. This hexane was removed under vacuum to provide the final complex as a bright orange powder. Yield: 176 mg (46%) MALDI-TOF MS (m/z): 727.5702 (calc.
  • Figure 17 shows the 1 H NMR spectrum of (L 4 ) 2 Ti(O i Pr) 2 in CDCb at 400 MHz.
  • Figure 18 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of MHz.
  • Figure 19 shows the ORTEP representation o crystallizes in the chiral orthorhombic space group Pna2i and adopts Type B coordination with one nitrogen trans to O'Pr and one detached, in favour of 0-0 coordination through the o-methoxy group. Due to the formation of a five-membered ring, the 0(1) - Ti - 0(2) bite angle is far more acute, at 72.92(8)°, than the 0(3) - Ti - N(2) bite angle, which is similar to that seen in (L 2 ) 2 Ti(O i Pr) 2 , at 80.72(9)°. Additionally, Ti - O'Pr distances are significantly shorter than in Type A by ca. 0.05 A, and the bound imine moiety is 0.02 A shorter than the unbound imine, which is expected.
  • Figure 20 shows the ORTEP representation of (L 5 ) 2 Ti(O i Pr) 2 .
  • (L 5 ) 2 Ti(O i Pr) 2 crystallizes in the centrosymmetric space group P2i/n and adopts Type B coordination with one nitrogen trans to O'Pr and one detached, in favour of 0-0 coordination through the o-methoxy group. Due to the formation of a five-membered ring, the 0(1) - Ti - 0(2) bite angle is far more acute, at 72.92(8)°, than the 0(3) - Ti - N(2) bite angle, which is similar to that seen in at 80.72(9)°. Additionally, Ti - O'Pr distances are significantly shorter than in Type A by ca. 0.05 A, and the bound imine moiety is 0.02 A shorter than the unbound imine, which is expected.
  • Hl_6 (1.193 g, 3.03 mmol) and Ti(O i Pr) 4 (0.429 g, 1.51 mmol) were dissolved separately in toluene (15 mL and 5 mL, respectively), and cooled to -30 °C in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo yielding a light yellow powder. Crude mixture was recrystallized by layering hexanes and THF. Yield: 1.29 g (90%) MALDI-TOF MS (m/z): 675.9662 (calc.
  • Figure 21 shows the 1 H NMR spectrum of (L 6 ) 2 Ti(O i Pr) 2 in CDCb at 400 MHz.
  • Figure 22 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 6 ) 2 Ti(O i Pr) 2 in CDCb at 125 MHz.
  • Figure 23 shows the ORTEP representation of (L 6 ) 2 Ti(O i Pr) 2 .
  • (L 6 ) 2 Ti(O i Pr) 2 crystallizes in a centrosymmetric space group and adopts Type C coordination, where steric bulk forces 0,0 chelation of both ligands.
  • (L6) 2 Ti(0'Pr) 2 shows O - Ti - O bite angles similar to those found in (L 4 ) 2 Ti(O i Pr) 2 at 73.67(5)° [0(1) - Ti - 0(2)] and 73.99(5)° [0(3) - Ti - 0(4)].
  • OVr moieties arrange trans to the neutral OMe groups and Ti - O'Pr distances are shorter than those found Type A and B complexes.
  • Figure 25 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 7 ) 2 T ⁇ (OPr) 2 in CDCb at 125 MHz.
  • Figure 26 shows the ORTEP representation of ⁇ L 7 ) 2 T ⁇ 0'Pr) 2 .
  • ⁇ L 7 ) 2 T ⁇ 0'Pr) 2 crystallizes in a centrosymmetric space group and adopts Type C coordination, where steric bulk forces 0,0 chelation of both ligands.
  • O'Pr moieties arrange trans to the neutral OMe groups and Ti - O'Pr distances are shorter than those found Type A and B complexes.
  • Hl_8 (2.04 g, 5.18 mmol) was suspended in toluene (20 mL) and THF (5 mL) and Ti(0'Pr)4 (0.736 g, 2.59 mmol) dissolved in toluene (5 mL) was added dropwise. The yellow suspension cleared after several minutes of stirring and allowed to react for 24 hours. Volatiles were removed in vacuo yielding a light yellow solid. Yield: 2.32 (94%) MALDI-TOF MS (m/z): 891.3367 (calc.
  • Figure 27 shows the ⁇ NMR spectrum of (L 8 ) 2 Ti(O i Pr) 2 in CDCb at 400 MHz.
  • Figure 28 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 8 ) 2 Ti(O i Pr) 2 in CDCb at 125 MHz.
  • Figure 29 shows the ORTEP representation of (L 8 ) 2 Ti(O i Pr) 2 .
  • (L 8 ) 2 Ti(O i Pr) 2 crystallizes in a centrosymmetric space group and adopts Type C coordination, where steric bulk forces 0,0 chelation of both ligands.
  • O'Pr moieties arrange trans to the neutral OMe groups and Ti - O'Pr distances are shorter than those found Type A and B complexes.
  • Hl_2 (0.40 g, 1.71 mmol) and K[N(SiMe 3 ) 2 ] (0.342 g, 1.71 mmol) were dissolved separately in THF (5 mL and 3 mL, respectively).
  • the K[N(SiMe3)2] solution was then added dropwise to the stirring solution of ligand and allowed to react for 24 hours.
  • ZrCU(THF) 2 (0.323 g, 0.857 mmol) was dissolved in THF (5 mL) and added to the deprotonated ligand. After stirring for 24 hours the resulting cloudy yellow solution was centrifuged and the solution was decanted.
  • Figure 30 shows the 1 H NMR spectrum of (L 2 )2ZrCI 2 in CDCb at 400 MHz.
  • HLs (0.246 g, 0.964 mmol) and K[N(SiMe 3 ) 2 ] (0.192 g, 0.964 mmol) were dissolved separately in THF (5 mL and 3 mL, respectively).
  • the K[N(SiMe3) 2 ] solution was then added dropwise to the stirring solution of ligand and allowed to react for 24 hours.
  • ZrCU(THF) 2 (0.182 g, 0.482 mmol) was dissolved in THF (5 mL) and added to the deprotonated ligand. After stirring for 24 hours the resulting cloudy yellow solution was centrifuged and the solution was decanted.
  • Figure 31 shows the 1 H NMR spectrum of (L 3 ) 2 ZrCI 2 in CDCb at 400 MHz.
  • Example 3 Crystallographic studies
  • Table 1 below provides a summary of the T- O distances in complexes (l_i)2Ti(0'Pr)2 -
  • Table 2 below provides select crystallographic details for (Li) 2 Ti(O i Pr) 2 - (L 4 )2Ti(O i Pr) 2 .
  • the ppm value of the 0,N imine resonance correlates closely with that seen in Type A complexes, -8.3 ppm, while the ppm value of the 0,0 resonance correlates to that seen in Type C complexes, -8.7 ppm. This indicates that the Type B coordination is retained in solution, and at room temperature signals are averaged due to dynamic exchange between ligands.
  • the standard conditions for carrying out the ethylene polymerisation process were as follows: In a glovebox, the immobilized catalyst (10 mg) was weighed into a thick walled ampule, along with triisobutylaluminum (TIBA, 150 mg), and hexane (50 ml_). The ampule was then cycled on to a Schlenk line and the N2 atmosphere was partially removed under vacuum. The slurry was heated to the desired temperature and stirred vigorously prior to the addition of ethylene at 2 bar. After the desired time had elapsed, the ampule was removed from heat and ethylene was removed from the system under vacuum and replaced with N2. The resulting polymer was filtered, washed several times with pentane, and dried.
  • TIBA triisobutylaluminum
  • hexane 50 ml_
  • Figure 40 shows the 1 H NMR spectrum of HL 4 ' in CDCb, 400 MHz.
  • Figure 41 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of HL 4 ' in CDCb, 400 MHz.
  • Figure 42 shows the ⁇ NMR spectrum of HL 5 ' in CDCb, 400 MHz.
  • Figure 43 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of HL 5 ' in CDCb, 400 MHz.
  • Figure 44 shows the ⁇ NMR spectrum of HL 6 ' in CDCb, 400 MHz.
  • Figure 45 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of HL 6 ' in CDCb, 400 MHz.
  • Figure 46 shows the ⁇ NMR spectrum of HL 7 ' in CDCb, 500 MHz. Synthesis of HLs'
  • Figure 47 shows the 1 H NMR spectrum of HL 4 F in CDCb, 400 MHz.
  • HI_4 F (0.50 g, 1.37 mmol) and (0.19 g, 0.68 mmol) were dissolved separately in toluene (5 ml_ and 5 ml_, respectively), and cooled to -30 °C in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo and hexane (10 ml_) was added to the resulting orange-yellow wax. This hexane was removed under vacuum to provide the final complex as a bright orange powder.
  • Figure 48 shows the 1 H NMR spectrum of [(L F 4 ) 2 Tl(O i Pr)d in CDCb, 400 MHz, as well as the 19 F ⁇ 1 H ⁇ NMR spectrum comparing HL F 4 (-58.1 ppm) and (-58.4) 400 MHz in CDCb.
  • Hl_4 (0.5 g, 1.61 mmol) and Ti(OEt) 4 (0.18 g, 0.80 mmol) were dissolved separately in toluene (10 ml_ and 10 ml_, respectively), and cooled to -30 °C in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo and hexane (10 ml_) was added to the resulting orange-yellow solid. This hexane was removed under vacuum to provide the final complex as a bright yellow powder (0.49 g, 0.65 mmol , 81 %).
  • Figure 49 shows the 1 H NMR spectrum of (L 4 ) 2 Ti(OEt) 2 in CDCb at 298 K.
  • Figure 50 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 4 ) 2 Ti(OEt) 2 in CDCb at 298 K.
  • HL 4 (2 eq.) and Ti(NMe2) 4 (1 eq) were dissolved separately in toluene (10 ml_ and 10 ml_, respectively), and cooled to -30 °C in a glovebox freezer. The two solutions were then mixed and allowed to stir for 24 hours. Volatiles were removed in vacuo and hexane (10 ml_) was added to the resulting red solid. Hexane was removed under vacuum to provide the final complex as a dark red powder. Crystals suitable for XRD were grown from slow evaporation of CDC . 1 H NMR was inconclusive, most likely due to fluxionality in the catalyst.
  • Figure 51 shows the ⁇ NMR spectrum of (L 4 ')2Tl(O i Pr)2 in CDCb at 298 K.
  • Figure 52 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of in CDCb at 298 K.
  • Figure 53 shows the 1 H NMR spectrum of in CDCb at 298 K.
  • Figure 54 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of (L 6 ')2Tl(O i Pr)2 in CDCb at 298 K.
  • Figure 55 shows the ⁇ NMR spectrum of (Le , )2 " n(O i Pr) 2 in CDCb at 298 K.
  • Figure 56 shows the 13 C ⁇ 1 H ⁇ NMR spectrum of in CDCb at 298 K.
  • Figure 57 shows the 1 H NMR spectrum of (L 7 ') 2 Ti(O i Pr) 2 in CDCb at 298 K. 400 MHz.
  • the initiating group on the titanium could be changed from isopropoxide to ethoxide or dimethylamide by changing the titanium precursor to Ti(OEt) 4 or Ti(NMe2) 4 , thus yielding (l_4)2Ti(OEt)2 and (l_4)2Ti(NMe2)2 respectively.
  • the structures of these compounds were confirmed using x-ray crystallography.
  • Figure 62 suggests that changing the steric bulk of the initiating group has an effect on the observed coordination type.
  • Amide catalysts (l_4-6')2Ti(0'Pr)2 were tested for ethylene polymerization in solution with MAO as an initiator and in the slurry phase after being preimmobilized on sMAO (according to the procedure described in Example 6).
  • Figure 63 illustrates the activity of the tested catalysts, as well as the morphology of the obtained polyethylene (PE). It is clear from Figure 63 that the PE produced on sMAO showed relatively uniform morphology in the SEM where the PE produced from solution phase polymerization was less uniform. The melting temperature of PE derived from slurry phase polymerization was uniformly higher than the corresponding solution phase polymerization. In addition, PE derived from slurry phase polymerization could be annealed through slow cooling cycles in order to increase the melt temperature of the final product by 2 - 3 °C (Table 5). Table 5 - Melt temperature of pre- and post-annealed polyethylenes prepared by slurry and solution phase polymerisation

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